Field desorption wire emitters

As field desorption (FD) refers to an experimental procedure in which a solution of the sample is deposited on the emitter wire situated at the tip of the FD insertion probe, it is suited for handling lubricants as well as polymer/additive dissolutions (without precipitation of the polymer or separation of the additive components). Field desorption is especially appropriate for analysis of thermally labile and high-MW samples. Considering that FD has a reputation of being difficult to operate and time consuming, and in view of recent competition with laser desorption methods, this is probably the reason that FD applications of polymer/additive dissolutions are not frequently being considered by experimentalists. 

Cl in conjunction with a direct exposure probe is known as desorption chemical ionization (DCI). [30,89,90] In DCI, the analyte is applied from solution or suspension to the outside of a thin resistively heated wire loop or coil. Then, the analyte is directly exposed to the reagent gas plasma while being rapidly heated at rates of several hundred °C s and to temperatures up to about 1500 °C (Chap. 5.3.2 and Fig. 5.16). The actual shape of the wire, the method how exactly the sample is applied to it, and the heating rate are of importance for the analytical result. [91,92] The rapid heating of the sample plays an important role in promoting molecular species rather than pyrolysis products. [93] A laser can be used to effect extremely fast evaporation from the probe prior to CL [94] In case of nonavailability of a dedicated DCI probe, a field emitter on a field desorption probe (Chap. 8) might serve as a replacement. [30,95] Different from desorption electron ionization (DEI), DCI plays an important role. [92] DCI can be employed to detect arsenic compounds present in the marine and terrestrial environment [96], to determine the sequence distribution of P-hydroxyalkanoate units in bacterial copolyesters [97], to identify additives in polymer extracts [98] and more. [99] Provided appropriate experimental setup, high resolution and accurate mass measurements can also be achieved in DCI mode. [100]... 

Giessmann, U. Heinen, H.J. Rollgen, F.W. Field Desorption of Nonelectrolytes Using Simply Activated Wire Emitters. Org. Mass Spectrom. 1979,14, 177-179. 

Figure 1. Electron micrograph of field desorption emitter prepared by activation of 10-n tungsten wire in a benzonitrile atmosphere. Distance between posts is 5 mm.

FAB is most often compared to the soft ionization method known as field desorption (FD) mass spectrometry, a technique in which the sample, deposited on an emitter wire coated with microcrystalline carbon needles, is desorbed under the influence of a high electric field gradient. As usual, bioorganic systems are best represented by both techniques (21, 33). Though FAB is the easier of the two, they are complementary, FAB being particularly suited for the case of extreme thermal lability and FD for the case of chemical lability or matrix interference. Cerny et al. (33) compare the two techniques for the study of coordination complexes and conclude FD is better for molecular-ion determination, while FAB provides better fragmentation information, which is useful in elucidating structures. 

In the field desorption technique (FD) the sample is placed on a specially prepared emitter wire and ionized in a high voltage electrostatic field. In this way little or no fragmentation occurs and mass peaks are obtained even from practically non-volatile peptides [34]. 

Field desorption (FD), pioneered by Beckey in 1969 [4], was the first and clearly the most successful of the early desorption ionization techniques. In the FD experiment, very high electric fields were used to extract ions from sample-coated thin wire emitters. FD spectra normally contained molecular weight information however, structural fragments were often absent and signal inslability resulted in data acquisition difficulties. As an added complication, FD was experimentally difficult and the method by which ions were formed was not well understood. 

The experimental technique for the trace analysis of metals simply involves the production of an emitter of acceptable quality. In general, 10 /im tungsten wires are activated at high temperature with benzonitrile in a multiple activation device. As the result of such an activation process, the tungsten wire is covered with dendrites of partially ordered pyrocarbon. Due to the small radii of curvature of the tips of the microneedles, the field strength is enhanced to a. level suitable for FDMS. These emitters are mechanically stable, which is important for repeated use they can also be chemically and thermally strained. This property is a prerequisite for the pyrolysis of the organic matrix and desorption of the metal cations, and last not least, the surface area of the emitter is sufficient for sample application. 

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